CN105734311B - A kind of magnetic refrigeration HoxTbyMzIt is high-entropy alloy and preparation method thereof - Google Patents

A kind of magnetic refrigeration HoxTbyMzIt is high-entropy alloy and preparation method thereof Download PDF

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CN105734311B
CN105734311B CN201610137032.5A CN201610137032A CN105734311B CN 105734311 B CN105734311 B CN 105734311B CN 201610137032 A CN201610137032 A CN 201610137032A CN 105734311 B CN105734311 B CN 105734311B
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entropy
entropy alloy
magnetic refrigeration
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CN105734311A (en
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吴渊
原园
吕昭平
童欣
袁小园
王辉
刘雄军
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University of Science and Technology Beijing USTB
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    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
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    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C28/00Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C30/00Alloys containing less than 50% by weight of each constituent

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Abstract

The invention belongs to the refrigeration alloy field of the magnetic in high entropy material, is related to a kind of magnetic refrigeration HoxTbyMzIt is high-entropy alloy and preparation method thereof, the chemical formula of the high-entropy alloy is HoxTbyMZ,The atomic percent of each composition is:5≤x≤35,5≤y≤35, wherein, M Gd, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Dy, one or more in Er, Tm, Yb, Lu and Y, 30≤z≤90, x+y+z=100, high entropy alloy material is formed under the conditions of conventional vacuum inhales casting, heat stagnation aftereffect is small, magnetic entropy with even more than metal Gd becomes and big magnetic refrigerant capacity, and highest refrigeration temperature area is excellent magnetic refrigerating material close in the range of room temperature up to 190K.Have a large capacity and a wide range household magnetic refrigerator, the daily life such as household magnetic air-conditioning, and national defence has broad application prospects and original purposes.

Description

A kind of magnetic refrigeration HoxTbyMzIt is high-entropy alloy and preparation method thereof
Technical field
The invention belongs to the magnetic cooling alloy field in functional material, and in particular to a kind of with big magnetic entropy change and magnetic system The Ho of cold energy powerxTbyMzIt is high entropy alloy material and preparation method thereof.
Background technology
Modern society human lives increasingly be unable to do without Refrigeration Technique, small to arrive daily life, such as domestic air conditioning, ice Case, foodstuffs refrigerator, air conditioning for automobiles, greatly to central air-conditioning, gas liquefaction, industrial and agricultural production etc..Used in traditional gas refrigeration Freon has destruction to atmospheric ozone layer, and currently used artificial synthesized Substitute Working Medium generally has strong greenhouse effects, hair Legally provide to stop using stage by stage up to country.Conventional refrigeration technology energy resource consumption simultaneously is big, and power consumption reaches society It is total to use 1/3rd or so of energy.Refrigerating efficiency is limited already close to the limit, energy-conservation.
The physical phenomenon absorbed heat that magnetothermal effect refers to magnetic material magnetic field-enhanced/being put when weakening/.In zero magnetic field condition Under, the orientation of magnetic moment is unordered in magnet, and now magnetic entropy is larger, and system adiabatic temperature is relatively low;After externally-applied magnetic field, magnetic moment is in magnetic Tend to be parallel with magnetic field under the moment loading of field, cause magnetic entropy to reduce, adiabatic temperature rises;When magnetic field diminishes, because magnetic is former The warm-up movement of son or ion, its magnetic moment tend to be unordered again, and adiabatic temperature reduces.Corresponding material is referred to as magnetic refrigerating material.Material The strong and weak of refrigerating capacity is generally become with the size of adiabatic temperature change with magnetic entropy to weigh.Meanwhile magnetic refrigerating material has a lot Advantage, 1. is green:The refrigeration working medium that uses of magnetic refrigeration is solid material, heat transfer medium water, eliminate CFCs, HCFC and What its substitute was brought damage the ozone layer, be poisonous, easy leakage, inflammable, greenhouse effects the defects of;It is 2. energy-efficient:Magnetic refrigeration Theoretical efficiency is up to the 60~70% of Carnot's cycle efficiency, and vapor compression refrigeration is generally 20~40%, opposing gas refrigeration Economize on electricity is up to 30%;It is 3. reliable and stable:Magnetic freezes without gas compressor, and moving component is few, and rotating speed is slow, vibration and noise It is small, small volume, long lifespan, reliability height.
Before cryomagnetic research can trace back to 120 years, Warburg is initially observed metallic iron in externally-applied magnetic field within 1881 Fuel factor.Early 20th century, displaying causes irreversible temperature to become to Langevin by changing the intensity of magnetization of paramagnetic material for the first time Change.Weiss and Piccard in 1915 has found Ni magnetothermal effect from experiment.Nineteen twenty-six Debye and nineteen twenty-seven Giauque After two scientists theoretically derive the conclusion that can utilize adiabatic demagnetization refrigeration respectively, magnetic refrigeration is greatly promoted Development.Hereafter the research of magnetic refrigeration is flourished.Extremely low temperature (tending to absolute 0K) and low temperature (<20K), medium temperature warm area Larger progress is achieved in terms of the research of (20K-77K) magnetic cooling material.But there is following three aspects in existing market Problem:
1) because high-entropy alloy is new metallic material, the invention magnetic refrigeration alloy not yet in high-entropy alloy series;
2) it is difficult to find the material with great magnetic entropy variation, or even the pure Gd of magnetic entropy no-load voltage ratio of many alloys also small;
3) larger financial burden can typically directly be caused by the use of rare earth element as magnetic working medium, its purification.
Due to above reason, it is difficult to meet current application requirement using existing magnetic refrigerating material, hinders magnetic material The further development of material;In addition, high-entropy alloy is as magnetic refrigerating material, using can be in wider temperature the characteristics of high-entropy alloy In the range of realize that big magnetic entropy becomes, and application can save cost in the form of high-entropy alloy by rare earth.Therefore research and develop The novel alloy for having big magnetic entropy to become in wide temperature range turns into the recent studies on direction in this field.
The content of the invention
Present invention is directed to magnetic entropy existing for current magnetic refrigerating material and becomes smaller, cost is higher and high-entropy alloy in do not send out A kind of the characteristics of bright magnetic refrigeration alloy, it is proposed that Ho with excellent magnetic refrigeration effectxTbyMzIt is high-entropy alloy and its preparation side Method.
The technical scheme is that:A kind of magnetic refrigeration HoxTbyMzIt is high-entropy alloy, the chemical formula of the high-entropy alloy is HoxTbyMz, wherein, 5≤x≤35,5≤y≤35, M Gd, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Dy, Er, Tm, Yb, Lu and Y In one or more, 30≤z≤90, x+y+z=100.
Further, work as x=20, y=20, M Gd, Dy and Er, z=60, then the chemical formula of the high-entropy alloy be Gd20Dy20Er20Ho20Tb20
Further, x=25 is worked as, y=25, M are Gd and Er, z=50, then the chemical formula of the high-entropy alloy is Gd25Er25Ho25Tb25
Further, x=33.33, y=33.34, M Er, z=33.33 are worked as, then the chemical formula of the high-entropy alloy is Er33.33Ho33.33Tb33.34
The magnetic property of alloy is also influenceed in addition to being influenceed by alloying component by alloy microstructure, usual single structure Alloy there is larger magnetic entropy to become.The magnetic refrigeration high-entropy alloy of the present invention uses vacuum arc melting furnace melting, direct pouring Shaping, technique are very simple.
It is a further object of the present invention to provide above-mentioned alloy preparation method to comprise the following steps:
Step 1:Using metallurgical raw material rare earth metal, accurate weighing proportioning is carried out according to mol ratio, alloy is prepared for melting Use;
Step 2:The surface scale of feed metal is removed using sand paper and abrasive machine, and is shaken using EtOH Sonicate ripple Swing cleaning feed metal;
Step 3:Using vacuum non-consumable tungsten electrode arc melting alloy, sample room is vacuumized, when vacuum reaches 5*10-3After Pa, technical argon is poured until furnace pressure reaches half of atmospheric pressure;
Step 4:In order that raw material is preferably well mixed in fusion process, after each molten alloy fusing, electric arc is kept Time 30s-60s, overturn after alloy block cooling, be so repeated 4 times the above;
Step 5:After the abundant melting of foundry alloy is uniform, using suction pouring equipment, alloy inspiration is entered into water cooled copper mould In, obtain high-entropy alloy rod.
Ho made of the preparation method of the present inventionxTbyMzIt is that magnetic cooling high-entropy alloy at least has under 5T externally-applied magnetic field (magnetic entropies of the simple metal Gd under 5T externally-applied magnetic field is changed into 9.8Jkg for magnetic entropy change equivalent to simple metal Gd-1K-1), and the conjunction The refrigerating capacity of gold is even greater than some giant magnetio-caloric effects materials, and its use temperature range is also close to the room temperature (magnetic that invention is related to The upper limit temperature in use of refrigeration high-entropy alloy is up to 190K), this is also exactly the emphasis that magnetic cooling material is studied at present, finds room temperature Magnetic cooling material.
Present invention advantage possessed compared with prior art is:
(1) formed by adjusting element, while the change of alloy system magnetic entropy is improved, moreover it is possible to maintain single-phase group of high-entropy alloy The characteristic knitted;
(2) because the rare earth element needed for high-entropy alloy is without purification, cost can largely be saved;
(3) high-entropy alloy not only there is big magnetic entropy to become, and the temperature range corresponding to maximum magnetic entropy variable half Width, there is high refrigerating capacity which results in the high-entropy alloy;
(4) broad application temperature range, and close to room temperature, ceiling temperature is up to 190K;
(5) compared with existing magnetic refrigerating material, the present invention for magnetic freeze high-entropy alloy, have magnetic refrigeration effect and meanwhile with The performance of high-entropy alloy.
Brief description of the drawings
Fig. 1 is three kinds of alloy embodiment Gd prepared by copper mold20Dy20Er20Ho20Tb20, Gd25Er25Ho25Tb25With Er33.33Ho33.33Tb33.34X-ray diffraction pattern.Abscissa is 2 θ angles (°);Ordinate is diffracted intensity (arbitrary unit).
Fig. 2 is a kind of embodiment alloy Gd of copper mold equipment20Dy20Er20Ho20Tb20Magnetic heating curve (externally-applied magnetic field For 3000Oe).Left side coordinate system is temperature (Kelvin);Ordinate is the intensity of magnetization (emu/g).
Fig. 3 is a kind of alloy embodiment Gd of copper mold equipment20Dy20Er20Ho20Tb20Isothermal magnetization curve.Horizontal seat It is designated as externally-applied magnetic field (tesla T);Ordinate is the intensity of magnetization (emu/g).
Fig. 4 is a kind of alloy embodiment Gd of copper mold equipment25Er25Ho25Tb25Isothermal magnetization curve.Abscissa is Externally-applied magnetic field (tesla T);Ordinate is the intensity of magnetization (emu/g).
Fig. 5 is three kinds of alloy embodiment Gd prepared by copper mold20Dy20Er20Ho20Tb20, Gd25Er25Ho25Tb25With Er33.33Ho33.33Tb33.34Magnetic entropy varied curve under 5T externally-applied magnetic field.Abscissa is temperature (Kelvin);Ordinate is magnetic Entropy Changes (Jkg-1K-1)。
Fig. 6 is a kind of alloy embodiment Gd of copper mold equipment20Dy20Er20Ho20Tb20Ratio dsc data.
Embodiment
With reference to specific embodiment pair the technical scheme is that being described further.
Embodiment
Using commercially available rare metal Gd, Er, Dy, Ho, Tb are parent material.Use vacuum non-consumable tungsten electricity arc melting Alloy, sample room is vacuumized, when vacuum reaches 5*10-3After Pa, technical argon is poured until furnace pressure reaches big half Air pressure;
After each molten alloy fusing, electric arc retention time 30s-60s, overturn after alloy block cooling, Mei Gehe Gold needs melting 4 times, to ensure that foundry alloy composition is uniform.The nominal composition (atomic percent) of embodiment alloy is respectively Gd20Dy20Er20Ho20Tb20, Gd25Er25Ho25Tb25And Er33.33Ho33.33Tb33.34.Appropriate foundry alloy material is taken to be positioned over logical Have in the copper mold of cooling water, alloy melt inhaled after electric arc furnaces refuse cast onto in the die cavity of copper mold under an argon atmosphere, Alloy melt is inhaled after electric arc furnaces refuse under an argon atmosphere and cast onto in the die cavity of copper mold.The die cavity of copper mold can basis Need to be designed to different sizes.It is Er by alloying component33.33Ho33.33Tb33.34And Gd25Er25Ho25Tb25Foundry alloy pour and build up 10mm*10mm high-entropy alloy rod.The X-ray diffraction spectrum of example cross section confirms the single-phase high entropy that whole sample is hcp structures Alloy, see Fig. 1.2mm*2mm*2mm is intercepted on the alloy bar for casting out and as sample from inhaling, it is public with U.S. Quantum Design The material comprehensive physical property measurement system (PPMS) of department's production measures the magnetic heating curve (M-T figures) of high entropy sample, and obtaining this is The magnetic order and antiferromagnetic transition temperature of row high-entropy alloy, are shown in Fig. 2.Then near magnetic order and antiferromagnetic transition temperature A series of isothermal magnetization curve M-H of measurement, are shown in Fig. 3 in certain temperature range.Thus isothermal magnetization curve combines following Maxwell relations, the magnetic entropy that can calculate alloy become.
During isothermal magnetization, the total magnetic entropy Δ S of systemMIt can be calculated using Maxwell's formula:
Wherein, and respectively the minimum and maximum value of applied magnetic field intensity is represented.We are in measurement process ,=5T, Integrate:
By measuring alloy in different temperatures TiUnder isothermal magnetization curve M-H, then existed using formula (2) computing system Different temperatures TiUnder magnetic entropy become Δ SM(as shown in Figure 3), it can be found that maximum magnetic entropy of the embodiment alloy under magnetic field intensity 5T Change has reached 9.917Jkg-1K-1, see Fig. 4, contrast magnetic entropies of the pure Gd under 5T and become (9.8Jkg-1K-1), it can be found that the alloy exists There is larger magnetic entropy to become within the scope of very wide temperature.
Here the size of the magnetic refrigerant capacity calculated be temperature range difference corresponding to the half value of maximum magnetic entropy variable one with most The product of great magnetic entropy variation value, table 1 are several embodiments of the present invention and the comparison of existing typical magnetic refrigerating material.It is possible thereby to Find out, this serial high-entropy alloy has excellent magnetic refrigeration performance.
Fig. 5 is the Gd measured20Dy20Er20Ho20Tb20The ratio dsc data of high-entropy alloy, differentiate that material becomes most in magnetic entropy with this What general goal occurred is first order phase change or second-order phase transistion on earth.Along with the material of first order phase change, it occurs bright than heating curve Aobvious spike, and similar λ smooth peak occurs in Fig. 5, it is similar with the material that second-order phase transistion occurs for Gd etc..Magnetic phase is occurring for material During change simultaneous structure change (first order phase change), fracture and fatigue easily occurs, influences it and uses the longevity bright, therefore we open The magnetic cooling high-entropy alloy of hair solves the problems, such as first order phase change material with having good while refrigeration effect is excellent Application prospect.
In summary, alloy provided by the present invention has big magnetic entropy to become within the scope of wider temperature, while also has There is the characteristic of high-entropy alloy, therefore the present invention is while the magnetic refrigeration effect of excellent performance is provided, there is provided one kind is based on The magnetic refrigerating material design of high-entropy alloy design concept.
Table 1 is under 5T externally-applied magnetic field, the embodiment of the present invention and the performance comparision of existing typical magnetic refrigerating material

Claims (6)

  1. The Ho 1. a kind of magnetic freezesxTbyMzIt is high-entropy alloy, it is characterised in that the chemical formula of the high-entropy alloy is HoxTbyMZ,Wherein, One kind or more in 5≤x≤35,5≤y≤35, M Gd, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Dy, Er, Tm, Yb and Lu Kind, 30≤z≤90, x+y+z=100.
  2. 2. according to claim 1 have magnetic refrigeration effect HoxTbyMzIt is high-entropy alloy, it is characterised in that as x=20, y= 20, M Gd, Dy and Er, z=60, then the chemical formula of the high-entropy alloy is Gd20Dy20Er20Ho20Tb20
  3. 3. according to claim 1 have magnetic refrigeration effect HoxTbyMzIt is high-entropy alloy, it is characterised in that as x=25, y= 25, M be Gd and Er, and z=50, then the chemical formula of the high-entropy alloy is Gd25Er25Ho25Tb25。
  4. 4. according to claim 1 have magnetic refrigeration effect HoxTbyMzBe high-entropy alloy, it is characterised in that when x= 33.33, y=33.34, M Er, z=33.33, then the chemical formula of the high-entropy alloy is Er33.33Ho33.33Tb33.34
  5. A kind of 5. magnetic refrigeration Ho prepared as described in claim any one of 1-4xTbyMzIt is the method for high-entropy alloy, its feature exists In including following steps:
    Step 1:Using metallurgical raw material rare earth metal, accurate weighing proportioning is carried out according to mol ratio, preparing alloy for melting uses;
    Step 2:The surface scale of feed metal is removed using sand paper and abrasive machine, and uses EtOH Sonicate ripple concussion cleaning Feed metal;
    Step 3:Using vacuum non-consumable tungsten electrode arc melting alloy, sample room is vacuumized, when vacuum reaches 5*10- 3After Pa, technical argon is poured until furnace pressure reaches half of atmospheric pressure;
    Step 4:After each molten alloy fusing, electric arc retention time 30s-60s, overturn after alloy block cooling, so It is repeated 4 times the above;
    Step 5:After the abundant melting of foundry alloy is uniform, using suction pouring equipment, alloy inspiration is entered in water cooled copper mould, obtained Magnetic refrigeration HoxTbyMzIt is high-entropy alloy.
  6. 6. according to the method for claim 5, it is characterised in that the magnetic refrigeration HoxTbyMzIt is that the upper limit of high-entropy alloy makes Reach 190K with temperature.
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CN108277416A (en) * 2017-12-25 2018-07-13 中国矿业大学 A kind of rare earth high-entropy alloy for magnetic refrigeration
CN109554602B (en) * 2018-12-28 2019-12-20 太原理工大学 High-entropy alloy with high-principal-element single-phase close-packed hexagonal structure and preparation method thereof
CN111825452B (en) * 2020-06-02 2022-09-06 航天材料及工艺研究所 Low-thermal-conductivity high-entropy aluminate ceramic and preparation method thereof
CN111719076A (en) * 2020-07-20 2020-09-29 桂林电子科技大学 Rare earth high-entropy alloy material with high saturation magnetization and preparation method thereof
CN115229144B (en) * 2022-08-05 2023-12-22 桂林电子科技大学 TbDyHoEr thin belt and preparation method and application thereof

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CN101067189A (en) * 2007-04-20 2007-11-07 北京科技大学 Gd-base magnetic cooling large block amorphous alloy
CN103602874B (en) * 2013-11-21 2016-03-02 北京科技大学 High strength low elastic modulus TiZrNbHf high-entropy alloy and preparation method
CN104946912B (en) * 2015-07-14 2017-04-26 太原理工大学 Rear earth high-entropy alloy of close-packed hexagonal structure

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